WO2021124855A1 - 粘着シート - Google Patents

粘着シート Download PDF

Info

Publication number
WO2021124855A1
WO2021124855A1 PCT/JP2020/044512 JP2020044512W WO2021124855A1 WO 2021124855 A1 WO2021124855 A1 WO 2021124855A1 JP 2020044512 W JP2020044512 W JP 2020044512W WO 2021124855 A1 WO2021124855 A1 WO 2021124855A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
adhesive sheet
sensitive adhesive
layer
weight
Prior art date
Application number
PCT/JP2020/044512
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
周作 上野
高正 平山
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020227020301A priority Critical patent/KR20220117232A/ko
Priority to CN202080088628.5A priority patent/CN114846098A/zh
Priority to JP2021565431A priority patent/JPWO2021124855A1/ja
Publication of WO2021124855A1 publication Critical patent/WO2021124855A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam

Definitions

  • the present invention relates to an adhesive sheet.
  • the adhesive sheet containing the heat-expandable microspheres has a predetermined adhesive strength, but the heat-expandable microspheres are expanded by heating to form irregularities on the adhesive surface to reduce the contact area. It is characterized by a decrease or disappearance of force.
  • Such an adhesive sheet has an advantage that the object to be treated can be easily peeled off without external stress.
  • the pressure-sensitive adhesive sheet containing the heat-expandable microspheres has low translucency, and when the pressure-sensitive adhesive sheet is used, the marking provided on the fixing base to indicate the temporary fixing position of the electronic component is visually recognized through the pressure-sensitive adhesive sheet. The problem arises that it is difficult.
  • the present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to achieve both excellent adhesiveness and peelability, and to be visible through an adherend (visualization through an adhesive sheet).
  • the purpose is to provide an adhesive sheet having excellent properties.
  • the pressure-sensitive adhesive sheet of the present invention includes a gas generating layer that generates gas by laser light irradiation, and has a haze value of 50% or less.
  • the thickness of the gas generating layer is 0.1 ⁇ m to 50 ⁇ m.
  • the gas generating layer is a layer capable of absorbing ultraviolet rays.
  • the gas generating layer comprises an ultraviolet absorber.
  • the pressure-sensitive adhesive sheet has an ultraviolet transmittance of 30% or less at a wavelength of 360 nm.
  • the pressure-sensitive adhesive sheet has an ultraviolet transmittance of 50% to 100% at a wavelength of 500 nm.
  • the gas generating layer is a layer that generates a hydrocarbon gas.
  • the gasification start temperature of the gas generation layer is 150 ° C. to 500 ° C.
  • the pressure-sensitive adhesive sheet has a 10% weight loss temperature of 200 ° C. to 500 ° C.
  • the pressure-sensitive adhesive sheet is further provided with a pressure-sensitive adhesive layer on at least one side of the gas-generating layer, and the pressure-sensitive adhesive layer is a layer whose surface is deformed by irradiating the pressure-sensitive adhesive sheet with laser light. is there.
  • the thickness of the pressure-sensitive adhesive layer is 0.1 ⁇ m to 50 ⁇ m.
  • the pressure-sensitive adhesive layer foams by irradiating the pressure-sensitive adhesive sheet with laser light.
  • a method of processing electronic components includes sticking the electronic component on the pressure-sensitive adhesive sheet and irradiating the pressure-sensitive adhesive sheet with laser light to peel off the electronic component from the pressure-sensitive adhesive sheet.
  • the electronic components are peeled off in a regioselective manner.
  • the treatment method comprises attaching the electronic component to the pressure-sensitive adhesive sheet and then performing a predetermined treatment on the electronic component before peeling the electronic component from the pressure-sensitive adhesive sheet. ..
  • the process is grinding, dicing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, alignment, repair or device surface protection. ..
  • a method of processing electronic components includes peeling the electronic component from the adhesive sheet and then arranging the electronic component on another sheet.
  • an adhesive sheet having both excellent adhesiveness and peelability and excellent visibility of an adherend (visibility through an adhesive sheet).
  • A. Summary view of a pressure-sensitive adhesive sheet 1 (a) is a schematic sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
  • the adhesive sheet 100 includes a gas generating layer 10.
  • the gas generation layer 10 generates gas by irradiation with laser light. More specifically, the gas generation layer 10 is a layer that generates gas by gasifying its components by laser light irradiation. As the laser light, UV laser light is typically used.
  • the gas generating layer 10 may have a predetermined adhesive force.
  • FIG. 1B is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention.
  • the pressure-sensitive adhesive sheet 100' includes a gas generation layer 10 and at least one pressure-sensitive adhesive layer 20 arranged on one side of the gas generation layer 10.
  • the surface of the pressure-sensitive adhesive layer 20 can be deformed by irradiating the pressure-sensitive adhesive sheet (substantially the gas generating layer) with laser light. In one embodiment, the deformation is due to the gas generated from the gas generating layer 10 and can occur on the opposite side of the pressure-sensitive adhesive layer 20 from the gas generating layer 10.
  • the pressure-sensitive adhesive sheet of the present invention can be used by attaching an object to be treated such as an electronic component to a gas generating layer or a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention includes a gas generating layer, and partially generates gas in a minute range by laser light irradiation. Such gas generation causes deformation of the sticking surface, and as a result, the adherend can be satisfactorily peeled off.
  • the pressure-sensitive adhesive sheet includes a pressure-sensitive adhesive layer, as described above, the pressure-sensitive adhesive layer is deformed due to the generation of the gas, and as a result, peelability is exhibited in the portion irradiated with the laser beam.
  • the laser beam is emitted from the side opposite to the pressure-sensitive adhesive layer of the gas generating layer.
  • the small electronic component can be satisfactorily peeled off even when processing (processing) an extremely fine small electronic component. Can be done. Even when a small electronic component that requires peeling and a small electronic component that does not require peeling are temporarily fixed next to each other, they should be peeled at the part to be peeled and not peeled at the part not to be peeled. That is, only the small electronic component that needs to be peeled can be peeled off, and unnecessary detachment of the small electronic component can be prevented.
  • it is preferable that at least a part of the generated gas is barriered so as not to come out of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive layer can function as a gas barrier layer.
  • Deformation of the pressure-sensitive adhesive layer means displacement that occurs in the normal direction (thickness direction) and the horizontal direction (direction orthogonal to the thickness direction) of the pressure-sensitive adhesive layer.
  • the deformation of the pressure-sensitive adhesive layer is caused by, for example, generating gas from the gas generating layer by pulse scanning at 0.80 mW output and frequency 40 kHz using UV laser light having a wavelength of 355 nm and a beam diameter of about 20 ⁇ m ⁇ .
  • the deformed shape is observed, for example, by measuring any one spot pulse-scanned 24 hours after the laser beam irradiation with a confocal laser scanning microscope or a non-contact interference microscope (WYKO).
  • the shape may be foam (convex), through hole (concavo-convex), or concave (concave), and these deformations can cause peelability.
  • the displacement change in the normal direction before and after laser light irradiation is large, and in particular, those having a foamed shape are suitable.
  • Foaming (convex) is defined as the vertical displacement Y at the highest point and the horizontal displacement X (diameter) at the full width at half maximum with reference to the surface of the adhesive sheet in the unirradiated portion.
  • the difference between the highest point and the lowest point is defined as the vertical displacement Y, and the diameter of the hole is defined as the horizontal displacement X.
  • the portion deformed by laser light irradiation is also referred to as a “deformed portion”.
  • FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention.
  • the pressure-sensitive adhesive sheet 200 further includes an intermediate layer 30 between the gas generating layer 10 and the pressure-sensitive adhesive layer 20.
  • the intermediate layer can function as a gas barrier layer in cooperation with the pressure-sensitive adhesive layer. Therefore, by providing the intermediate layer, the gas barrier property is improved, and a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is deformed can be obtained more preferably.
  • the intermediate layer may be a single layer or a plurality of layers.
  • the adhesive sheet may further include other layers.
  • a base material for example, a base material, another pressure-sensitive adhesive layer, or the like may be provided on the surface of the gas generating layer opposite to the pressure-sensitive adhesive layer.
  • the base material for example, a film formed from any suitable resin is used.
  • the adhesive sheet of the present invention is characterized in that the haze value is 50% or less.
  • the gas generating layer, the pressure-sensitive adhesive layer and the intermediate layer can be formed without containing an insoluble filler or the like, the pressure-sensitive adhesive sheet has a small haze value, high translucency, and suppressed white turbidity. Can be obtained.
  • the adhesive sheet has high transparency before laser irradiation (temporarily fixed).
  • an adherend for example, a base for temporarily fixing an electronic component
  • the marking provided on the fixed base can be preferably visually recognized through the adhesive sheet.
  • Such an effect is an excellent effect that cannot be obtained with a pressure-sensitive adhesive sheet containing an insoluble filler (for example, a pressure-sensitive adhesive sheet containing heat-expandable microspheres in a pressure-sensitive adhesive layer as a peelable expression layer).
  • a pressure-sensitive adhesive sheet containing an insoluble filler for example, a pressure-sensitive adhesive sheet containing heat-expandable microspheres in a pressure-sensitive adhesive layer as a peelable expression layer.
  • the haze value of the pressure-sensitive adhesive sheet of the present invention is preferably 0% to 50%, more preferably 0.01% to 40%, still more preferably 0.05% to 30%, and particularly preferably 0. .1% to 20%. Within such a range, the above-mentioned effect of the present invention becomes more remarkable.
  • the adhesive strength of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention to SUS430 is preferably 0.1 N / 20 mm or more, more preferably 0.2 N / 20 mm to 50 N / 20 mm, and further preferably 0.5 N / 20 mm. It is ⁇ 40N / 20mm, particularly preferably 0.7N / 20mm to 20N / 20mm, and most preferably 1N / 20mm to 10N / 20mm. Within such a range, for example, an adhesive sheet exhibiting good adhesiveness can be obtained as a temporary fixing sheet used for manufacturing electronic parts.
  • the adhesive strength is measured in an environment of 23 ° C. by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °). Adhesive strength.
  • the gas generating layer has a predetermined adhesive force.
  • the adhesive strength of the gas generating layer of the pressure-sensitive adhesive sheet of the present invention to SUS430 is preferably 0.1 N / 20 mm or more, more preferably 0.5 N / 20 mm to 50 N / 20 mm, and further preferably 1 N / 20 mm to 40 N. / 20 mm, particularly preferably 1.5N / 20mm to 30N / 20mm, and most preferably 2N / 20mm to 20N / 20mm. Within such a range, for example, an adhesive sheet exhibiting good adhesiveness can be obtained as a temporary fixing sheet used for manufacturing electronic parts.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 2 ⁇ m to 200 ⁇ m, more preferably 3 ⁇ m to 150 ⁇ m, and further preferably 5 ⁇ m to 120 ⁇ m.
  • Water vapor permeability of the pressure-sensitive adhesive sheet of the present invention is preferably not 5000g / (m 2 ⁇ day) or less, more preferably 4800g / (m 2 ⁇ day) or less, more preferably 4500g / (m 2 ⁇ day ) Or less, more preferably 4200 g / (m 2 ⁇ day) or less.
  • the pressure-sensitive adhesive sheet provided with the pressure-sensitive adhesive layer (further intermediate layer if necessary) having a water vapor transmittance in such a range gas escape caused by laser light irradiation is prevented, and the pressure-sensitive adhesive layer has an excellent shape. A deformed portion is formed.
  • a small adherend for example, an electronic component
  • the water vapor permeability can be measured by a measuring method based on JIS K7129B in an atmosphere of 30 ° C. and 90% RH.
  • Water vapor permeability of the laminate of the adhesive layer and the intermediate layer is preferably not 10000g / (m 2 ⁇ day) or less, more preferably 7000g / (m 2 ⁇ day) or less, more preferably 5000g / (m 2 ⁇ day) or less, further preferably 4800 g / (m 2 ⁇ day) or less, particularly preferably 4500 g / (m 2 ⁇ day) or less, and most preferably 4200g / (m 2 ⁇ day) or less.
  • the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer.
  • a small adherend for example, an electronic component
  • Water vapor permeability of laminate comprising a pressure-sensitive adhesive layer and the intermediate layer is preferably as small, its lower limit is, for example, 1g / (m 2 ⁇ day) .
  • the piercing strength of the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer is preferably 10 mN to 5000 mN, more preferably 30 mN to 4000 mN, further preferably 50 mN to 3000 mN, and particularly preferably 100 mN to 2000 mN. ..
  • the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer functions well as a gas barrier layer, and the shape change is preferably caused by gas generation.
  • the shape of the pressure-sensitive adhesive layer is deformed excellently.
  • the part is formed.
  • a small adherend for example, an electronic component
  • the piercing strength was measured by using a compression tester 6 (manufactured by Kato Tech Co., Ltd., trade name “KES-G5”) in sample holders 5A and 5B having a circular opening with a diameter of 11.28 mm. 4 (for example, a laminated body) is held and measured. More specifically, at a measurement temperature of 23 ° C., a piercing needle (radius of curvature: 1 mm) is pierced into the sample (piercing speed: 0.1 mm / s) at the center of the circular opening of the circular opening at the fracture point. The maximum load can be the piercing strength.
  • the ultraviolet transmittance of the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer at a wavelength of 360 nm is preferably 50% to 100%, more preferably 60% to 95%.
  • the ultraviolet transmittance of the pressure-sensitive adhesive sheet at a wavelength of 360 nm is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, particularly preferably 10% or less, and most preferably. It is 5% or less.
  • the lower limit of the ultraviolet transmittance of the pressure-sensitive adhesive sheet at a wavelength of 360 nm is, for example, 0% (preferably 0.05%, more preferably 0.1%).
  • the ultraviolet transmittance of the pressure-sensitive adhesive sheet at a wavelength of 500 nm is preferably 50% to 100%, more preferably 60% to 99%, further preferably 70% to 98%, and particularly preferably 80% to 80%. It is 97%.
  • the 10% weight loss temperature of the pressure-sensitive adhesive sheet is preferably 200 ° C. to 500 ° C., more preferably 220 ° C. to 450 ° C., further preferably 250 ° C. to 400 ° C., and particularly preferably 270 ° C. to 370 ° C. °C. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the 10% weight loss temperature of the pressure-sensitive adhesive sheet was reduced by 10% by weight with respect to the weight before the temperature rise in the TGA analysis when the temperature of the pressure-sensitive adhesive sheet was raised (that is, the weight of the pressure-sensitive adhesive sheet was reduced with respect to the weight before irradiation. It means the temperature at the time (which became 90%).
  • the gas generating layer can be a layer capable of absorbing ultraviolet rays.
  • the gas generating layer comprises a UV absorber.
  • the ultraviolet absorber By containing the ultraviolet absorber, it is possible to form a gas generating layer capable of absorbing laser light and gasifying it.
  • the gas generating layer contains an ultraviolet absorber and an adhesive A.
  • the UV absorber is present dissolved in the pressure-sensitive adhesive A. If the ultraviolet absorber is dissolved in the pressure-sensitive adhesive A and exists, a deformed portion (for example, an uneven portion) is generated at any portion of the sticking surface (gas generating layer surface and / or pressure-sensitive adhesive layer surface).
  • the state of "dissolved in the pressure-sensitive adhesive” means that the ultraviolet absorber does not exist as particles in the gas generating layer. More specifically, it is preferable that the gas generating layer does not contain an ultraviolet absorber having a particle diameter of 10 ⁇ m or more in the particle distribution measurement in the cross section of the gas generating layer by X-ray CT.
  • the gas generating layer may or may not contain an insoluble component in the pressure-sensitive adhesive.
  • the presence / absence and content of the insoluble component in the gas generating layer is evaluated by the haze value of the gas generating layer, and the smaller the haze value, the smaller the content of the insoluble component in the gas generating layer. Be evaluated.
  • the gas generating layer is substantially free of adhesive-insoluble components.
  • the elastic modulus of the cross section of the gas generating layer by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, the shape of the gas generating layer is preferably changed due to gas generation, and as a result, a deformed portion having an excellent shape is formed on the adhesion surface (the surface of the gas generating layer and / or the surface of the pressure-sensitive adhesive layer).
  • the elastic modulus by the nanoindentation method is obtained by continuously measuring the load on the indenter and the pressing depth when the indenter is pushed into the sample (for example, the adhesive surface) during loading and unloading. Load load-The elastic modulus obtained from the indentation depth curve.
  • the elastic modulus by the nanoindentation method is the displacement-load hysteresis curve obtained by pressing a diamond Berkovich type (triangular pyramid type) probe perpendicularly to the cut section of the measurement target layer, and the software attached to the measuring device. It is obtained by numerical processing with (triboscan).
  • the elastic modulus of the cross section by the nanoindentation method refers to the elastic modulus of the cross section by a single indentation method at a predetermined temperature (25 ° C.) using a nanoindenter (Titanium Inc. Triboinder TI-950).
  • the elastic modulus of the gas generating layer can be adjusted by the type of material contained in the corresponding layer, the structure of the base polymer constituting the material, the type and amount of the additive added to the corresponding layer, and the like. ..
  • the elastic modulus by the nanoindentation method does not mean the cross section or the surface, and the elastic modulus means the elastic modulus by the nanoindentation method of the cross section.
  • the elastic modulus of the surface of the gas generating layer by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, the shape of the gas generating layer is preferably changed due to gas generation, and as a result, a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer.
  • the elastic modulus by the nanoindentation method is obtained by continuously measuring the load on the indenter and the pressing depth when the indenter is pushed into the sample (for example, the adhesive surface) during loading and unloading. Load load-The elastic modulus obtained from the indentation depth curve.
  • the elastic modulus by the nanoindentation method is the displacement-load hysteresis curve obtained by pressing a diamond Berkovich type (triangular pyramid type) probe perpendicularly to the cut section of the measurement target layer, and the software attached to the measuring device. It is obtained by numerical processing with (triboscan).
  • the elastic modulus of the surface by the nanoindentation method refers to the elastic modulus of the surface by a single indentation method at a predetermined temperature (25 ° C.) using a nanoindenter (Titanium Inc. Triboinder TI-950).
  • the elastic modulus was measured under the measurement conditions of 500 nm / sec, a pull-out speed of about 500 nm / sec, and a pushing depth of about 3000 nm.
  • the elastic modulus of the gas generating layer can be adjusted by the type of material contained in the corresponding layer, the structure of the base polymer constituting the material, the type and amount of the additive added to the corresponding layer, and the like. ..
  • the gasification start temperature of the gas generation layer is preferably 150 ° C. to 500 ° C., more preferably 170 ° C. to 450 ° C., further preferably 190 ° C. to 420 ° C., and particularly preferably 200 ° C. to 400 ° C. °C. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the gasification start temperature of the gas generation layer means the gas generation rise temperature calculated from the EGA analysis when the temperature of the pressure-sensitive adhesive sheet is raised.
  • the gas generation rise temperature is defined as the temperature at which half of the maximum gas generation peak in the EGA / MS spectrum obtained from EGA analysis is reached.
  • the gasification start temperature of the gas generating layer corresponds to the gasification start temperature of the ultraviolet absorber.
  • the 10% weight loss temperature of the gas generating layer is preferably 150 ° C. to 500 ° C., more preferably 170 ° C. to 450 ° C., and further preferably 200 ° C. to 400 ° C. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the 10% weight reduction temperature of the gas generation layer means that the weight of the gas generation layer is the weight before the temperature rise in the TGA analysis when the temperature of the pressure-sensitive adhesive sheet is raised (for example, when the temperature is raised by laser light irradiation). It means the temperature at the time when the weight of the gas generating layer is reduced by 10% by weight (that is, the weight of the gas generating layer becomes 90% with respect to the weight before the temperature rise).
  • the thickness of the gas generating layer is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 40 ⁇ m, further preferably 2 ⁇ m to 30 ⁇ m, and particularly preferably 5 ⁇ m to 20 ⁇ m. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: ⁇ m] of the gas generating layer by the nanoindentation method satisfy the following formula (1).
  • the gas generating layer is configured to satisfy the above formula (1), excessive deformation due to the gas generated from the gas generating layer is prevented, and the adhesive sheet is satisfactorily formed by laser light irradiation. Deform.
  • a thick barrier layer as a layer for preventing excessive deformation. More specifically, the surface of the gas generating layer alone can be deformed, or the pressure-sensitive adhesive layer (gas barrier layer) can be flexibly configured.
  • the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: ⁇ m] by the nanoindentation method satisfy the following formula (2).
  • the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: ⁇ m] by the nanoindentation method satisfy the following formula (3).
  • Log (Er (gas) ⁇ 10 6 ) ⁇ 7.52 ⁇ h (gas) -0.081 ... (3) Within such a range, the above effect becomes more remarkable.
  • the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: ⁇ m] by the nanoindentation method further satisfy the following formula (4).
  • the ultraviolet transmittance of the gas generating layer at a wavelength of 360 nm is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, particularly preferably 10% or less, and most preferably. Is less than 5%.
  • the lower limit of the ultraviolet transmittance of the gas generating layer at a wavelength of 360 nm is, for example, 0% (preferably 0.05%, more preferably 0.1%).
  • the haze value of the gas generating layer is preferably 55% or less, more preferably 0.1% to 50%, and further preferably 0.5% to 40%.
  • the haze value is an index of compatibility between the pressure-sensitive adhesive (substantially the base polymer) in the gas generating layer and the ultraviolet absorber.
  • the haze value is obtained from the ratio of diffuse transmitted light to total light transmitted light when light in the visible light region (wavelength: 380 nm to 780 nm) is incident.
  • the wavelength size of light is regarded as the minimum unit and the density and composition are uniform above the wavelength size, the transparency is high, that is, the compatibility is high.
  • the ultraviolet absorber can be an adhesive sheet formed by being present evenly. Such an adhesive sheet accurately exhibits peelability by irradiating with laser light.
  • UV absorber any suitable ultraviolet absorber can be used as long as the effects of the present invention can be obtained.
  • the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. Of these, a triazine-based ultraviolet absorber is preferable.
  • a triazine-based ultraviolet absorber can be preferably used because the acrylic pressure-sensitive adhesive has high compatibility with the base polymer.
  • the triazine-based ultraviolet absorber is more preferably composed of a compound having a hydroxyl group, and particularly preferably an ultraviolet absorber composed of a hydroxyphenyltriazine-based compound (hydroxyphenyltriazine-based ultraviolet absorber).
  • hydroxyphenyltriazine-based ultraviolet absorber examples include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hydroxyphenyl and [(C10). -C16 (mainly C12-C13) alkyloxy) methyl] Reaction product with oxylane (trade name "TINUVIN 400", manufactured by BASF), 2- [4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4) Reaction product of -dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis (2-hydroxy-4) -Butoxyphenyl
  • benzotriazole-based ultraviolet absorber examples include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF) and benzene.
  • Ester compounds of propanoic acid and 3- (2H-benzotriazole-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (trade name "TINUVIN 384") -2 ", manufactured by BASF), Octyl 3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [ 3-tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2yl) phenyl] propionate mixture (trade name "TINUVIN 109", manufactured by BASF), 2- (2H-benzotriazole) -2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 900", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -6- (1-Met
  • a halogen atom-free UV absorber is used. By using such an ultraviolet absorber, it is possible to obtain an adhesive sheet that does not easily contaminate an adherend such as an electrode.
  • the molecular weight of the compound constituting the ultraviolet absorber is preferably 200 to 1500, more preferably 250 to 1200, and further preferably 300 to 1000. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the maximum absorption wavelength of the ultraviolet absorber is preferably 300 nm to 450 nm, more preferably 320 nm to 400 nm, and further preferably 330 nm to 380 nm.
  • the content ratio of the ultraviolet absorber is preferably 1 part by weight to 100 parts by weight, more preferably 1 part by weight to 50 parts by weight, and further preferably 5 parts by weight with respect to 100 parts by weight of the gas generating layer. ⁇ 30 parts by weight. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.
  • the pressure-sensitive pressure-sensitive adhesive A is preferably used as the pressure-sensitive adhesive A contained in the gas generating layer.
  • the pressure-sensitive adhesive A for example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, vinyl alkyl ether-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, polyamide-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, and styrene-diene block are all used. Polymerization system adhesives, etc. may be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable.
  • the pressure-sensitive adhesive may be used alone or in combination of two or more.
  • the acrylic pressure-sensitive adhesive includes, for example, an acrylic pressure-sensitive adhesive based on an acrylic polymer (homopolymer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component. And so on.
  • Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth).
  • a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms can be preferably used, and a linear or branched alkyl group having 2 to 20 carbon atoms can be preferably used.
  • (Meta) acrylic acid alkyl esters having the above can be more preferably used.
  • a (meth) acrylic acid alkyl ester A having a linear or branched alkyl group having 4 or more carbon atoms (preferably 4 to 20, more preferably 4 to 18) is used.
  • An acrylic polymer formed by using such a monomer and having a long side chain is advantageous in that it has a high affinity (compatibility) with an ultraviolet absorber.
  • the content ratio of the (meth) acrylic acid alkyl ester A is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight, based on all the constituent units constituting the acrylic polymer. It is from% by weight to 100% by weight, and particularly preferably 80% by weight to 100% by weight.
  • the content ratio of the acrylic polymer containing the structural unit derived from the (meth) acrylic acid alkyl ester A is preferably 30 parts by weight to 100 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer. It is 70 parts by weight to 100 parts by weight.
  • a triazine-based (meth) acrylic acid alkyl ester A having a linear or branched alkyl group having 4 or more carbon atoms (preferably 4 to 20, more preferably 4 to 18). Used in combination with UV absorbers.
  • the (meth) acrylic acid alkyl ester A and the triazine-based ultraviolet absorber are particularly excellent in compatibility, and the pressure-sensitive adhesive sheet provided with the gas generating layer formed by using these compounds is remarkably excellent in visibility.
  • the acrylic polymer is a unit corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance, crosslinkability, etc. May include.
  • monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride.
  • Acid anhydride monomers such as; (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyoctyl acrylate, (meth) Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropan sulfonic acid.
  • Aminoalkyl (meth) acrylate monomers such as aminoethyl and t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
  • Maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconimide-based monomers; N- (meth) acryloyloxymethylene succinimide, N- (meth) accurloyl-6-oxyhexamethylene succinimide, Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyro Vinyls
  • Acrylic acid ester-based monomers having the above; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol Polyfunctional monomers such as di (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin-based monomers such as isobutylene; vinyl ether-based monomers such as vinyl ether and the like can be mentioned.
  • These monomer components may be used alone or in combination of two or more.
  • carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid from the viewpoint of high affinity (compatibility) with ultraviolet absorbers; anhydrous.
  • Acid anhydride monomers such as maleic acid and icotanic acid anhydride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, (meth) acrylic acid Hydroxyl group-containing monomers such as hydroxyoctyl, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methylmethacrylate are preferably used.
  • the content ratio of the carboxyl group-containing monomer is preferably 0.5 parts by weight to 15 parts by weight, more preferably 1 part by weight to 10 parts by weight, still more preferably, based on 100 parts by weight of the total amount of the acrylic polymer. It is 3 parts by weight to 9.5 parts by weight.
  • the content ratio of the acid anhydride monomer is preferably 0.5 parts by weight to 15 parts by weight, more preferably 1 part by weight to 10 parts by weight, still more preferably, based on 100 parts by weight of the total amount of the acrylic polymer. It is 3 parts by weight to 9.5 parts by weight.
  • the content ratio of the hydroxyl group-containing monomer is preferably 0.5 parts by weight to 15 parts by weight, more preferably 1 part by weight to 10 parts by weight, still more preferably, based on 100 parts by weight of the total amount of the acrylic polymer. It is 3 parts by weight to 9.5 parts by weight.
  • the rubber-based pressure-sensitive adhesive examples include natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, and styrene-butadiene.
  • SBS styrene block copolymer
  • SEBS styrene / ethylene / butylene / styrene block copolymer
  • SEPS styrene / ethylene / propylene block copolymer
  • SEP rubber-based pressure-sensitive adhesives based on polymer
  • SEP recycled rubber, butyl rubber, polyisobutylene, synthetic rubber such as modified products thereof
  • the gas generated from the gas generation layer is preferably a hydrocarbon (preferably an aliphatic hydrocarbon) -based gas.
  • the gas generating layer capable of generating a hydrocarbon-based gas is composed of, for example, a hydrocarbon-based compound as a main component.
  • the gas generation layer preferably does not contain a compound containing a halogen element. If the generated gas is a hydrocarbon-based gas, it is possible to prevent corrosion of electronic parts that are workpieces. Such an effect becomes more remarkable by forming a gas generating layer containing no compound containing a halogen element.
  • the amount of generated ions from the gas generating layer is preferably 10 m / z to 800 m / z, more preferably 11 m / z to 700 m / z, still more preferably 12 m / z to 500 m / z, and particularly. It is preferably 13 m / z to 400 m / z.
  • the pressure-sensitive adhesive A may contain any suitable additive, if necessary.
  • the additive include a cross-linking agent, a tackifier (for example, a rosin-based tackifier, a terpene-based tackifier, a hydrocarbon-based tackifier, etc.), and a plasticizer (for example, a trimellitic acid ester-based plasticizer). , Pyromellitic acid ester plasticizer), pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, etc. ..
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metals.
  • examples thereof include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents. Of these, an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent is preferable.
  • isocyanate-based cross-linking agent examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L”), tri Methylolpropane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), is
  • the content of the isocyanate-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.1 to 20 parts by weight with respect to 100 parts by weight of the base polymer. It is more preferably 0.5 parts by weight to 10 parts by weight.
  • epoxy-based cross-linking agent examples include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-glycidyl aminomethyl) cyclohexane (Mitsubishi Gas).
  • the content of the epoxy-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the base polymer. It is more preferably 0.03 part by weight to 5 parts by weight.
  • the adhesive layer comprises any suitable adhesive B.
  • the pressure-sensitive adhesive B may be a pressure-sensitive pressure-sensitive adhesive B1 or a curable pressure-sensitive adhesive B2.
  • the thickness of the pressure-sensitive adhesive layer is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.5 ⁇ m to 40 ⁇ m, further preferably 1 ⁇ m to 30 ⁇ m, and particularly preferably 2 ⁇ m to 20 ⁇ m. Within such a range, it is possible to form an adhesive layer having a preferable adhesive force and functioning well as a gas barrier layer.
  • Water vapor permeability of the adhesive layer is preferably not 20000g / (m 2 ⁇ day) or less, more preferably 10000g / (m 2 ⁇ day) or less, more preferably 7000g / (m 2 ⁇ day) It is less than or equal to, more preferably 5000 g / (m 2 ⁇ day) or less, particularly preferably 4800 g / (m 2 ⁇ day) or less, and most preferably 4500 g / (m 2 ⁇ day) or less.
  • the pressure-sensitive adhesive layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed.
  • a small adherend for example, an electronic component
  • the piercing strength of the pressure-sensitive adhesive layer is preferably 10 mN to 3000 mN, more preferably 30 mN to 2500 mN, further preferably 50 mN to 2000 mN, and particularly preferably 100 mN to 2000 mN.
  • the pressure-sensitive adhesive layer functions well as a gas barrier layer, and the shape change due to gas generation preferably occurs, and as a result, a deformed portion having an excellent shape is formed.
  • a small adherend for example, an electronic component
  • the ultraviolet transmittance of the pressure-sensitive adhesive layer at a wavelength of 360 nm is preferably 50% to 100%, more preferably 60% to 95%.
  • Pressure-sensitive adhesive B1 examples include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, and styrene-. Dienblock copolymer system adhesives and the like can be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable. As the pressure-sensitive adhesive B1 contained in the pressure-sensitive adhesive layer containing the pressure-sensitive pressure-sensitive adhesive, the pressure-sensitive adhesive described in Section B-2 can be used.
  • curing adhesive B2 examples include a thermosetting type pressure-sensitive adhesive and an active energy ray-curable pressure-sensitive adhesive.
  • an active energy ray-curable pressure-sensitive adhesive is used.
  • the pressure-sensitive adhesive layer formed by the active energy ray-curable pressure-sensitive adhesive is a pressure-sensitive adhesive layer formed by irradiating the active energy ray, that is, a pressure-sensitive adhesive layer having a predetermined adhesive strength after irradiation with the active energy ray. Is.
  • Examples of the resin material constituting the active energy ray-curable pressure-sensitive adhesive include an ultraviolet curing system (written by Kiyomi Kato, published by the General Technology Center (1989)), a photocuring technology (edited by the Technical Information Association (2000)), and special features. Examples thereof include resin materials described in Kai 2003-292916, Japanese Patent No. 4151850, and the like. More specifically, a resin material (B2-1) containing a polymer serving as a base material and an active energy ray-reactive compound (monomer or oligomer), a resin material containing an active energy ray-reactive polymer (B2-2), and the like. Can be mentioned.
  • polymer serving as the base material examples include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, butyl rubber, polyisobutylene rubber, and nitrile rubber (NBR).
  • NBR nitrile rubber
  • examples include rubber-based polymers; silicone-based polymers; acrylic-based polymers. These polymers may be used alone or in combination of two or more.
  • the active energy ray-reactive compound examples include a photoreactive monomer or oligomer having a plurality of functional groups having carbon-carbon multiple bonds such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group. .. Among them, a compound having an ethylenically unsaturated functional group is preferably used, and a (meth) acrylic compound having an ethylenically unsaturated functional group is more preferably used. Since a compound having an ethylenically unsaturated functional group easily generates radicals by ultraviolet rays, it is possible to form a pressure-sensitive adhesive layer that can be cured in a short time by using the compound.
  • a photoreactive monomer or oligomer having a plurality of functional groups having carbon-carbon multiple bonds such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an ace
  • a pressure-sensitive adhesive layer having an appropriate hardness can be formed after curing.
  • the photoreactive monomer or oligomer include trimethyl propantri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol.
  • examples thereof include (meth) acryloyl group-containing compounds such as (meth) acrylate-based compounds; and 2 to pentamers of the (meth) acryloyl group-containing compound. These compounds may be used alone or in combination of two or more.
  • the active energy ray-reactive compound a monomer such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinyl siloxane; or an oligomer composed of the monomer may be used.
  • the resin material (B2-1) containing these compounds can be cured by high-energy rays such as ultraviolet rays and electron beams.
  • the active energy ray-reactive compound a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule may be used.
  • the organic salt is cleaved by irradiation with active energy rays (for example, ultraviolet rays and electron beams) to generate ions, which act as a starting species to cause a ring-opening reaction of a heterocycle to form a three-dimensional network structure.
  • active energy rays for example, ultraviolet rays and electron beams
  • examples of the organic salts include iodonium salt, phosphonium salt, antimonium salt, sulfonium salt, borate salt and the like.
  • the heterocycle in the compound having a plurality of heterocycles in the molecule include oxylane, oxetane, oxolane, thiirane, and aziridine.
  • the content ratio of the active energy ray-reactive compound is preferably relative to 100 parts by weight of the polymer as the base material. It is 0.1 parts by weight to 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, and further preferably 10 parts by weight to 200 parts by weight.
  • the active energy ray-reactive polymer examples include a polymer having an active energy ray-reactive functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group.
  • a compound (polymer) having an ethylenically unsaturated functional group is used, and more preferably, a (meth) acrylic polymer having an acryloyl group or a methacryloyl group is used.
  • Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate.
  • the polymer composed of the polyfunctional (meth) acrylate preferably has an alkyl ester having 4 or more carbon atoms in a side chain, more preferably has an alkyl ester having 6 or more carbon atoms, and has 8 carbon atoms. It is more preferable to have the above alkyl ester, it is particularly preferable to have an alkyl ester having 8 to 20 carbon atoms, and most preferably to have an alkyl ester having 8 to 18 carbon atoms.
  • the resin material (B2-2) containing the active energy ray-reactive polymer may further contain the active energy ray-reactive compound (monomer or oligomer).
  • the active energy ray-curable pressure-sensitive adhesive can be cured by irradiation with active energy rays.
  • the adherend can be adhered by sticking the adherend before curing the pressure-sensitive adhesive and then irradiating the pressure-sensitive adhesive with active energy rays to cure the pressure-sensitive adhesive.
  • the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like.
  • Conditions such as the wavelength of the active energy ray and the irradiation amount can be set to arbitrary appropriate conditions according to the type of resin material used and the like.
  • the pressure-sensitive adhesive can be cured by irradiating with ultraviolet rays having an irradiation amount of 10 to 1000 mJ / cm 2.
  • Intermediate layer examples of the form of the intermediate layer include a resin layer and an adhesive layer.
  • the intermediate layer contains a thermoplastic resin.
  • a thermoplastic resin such an intermediate layer may be a resin film containing a thermoplastic resin, a layer containing a pressure-sensitive adhesive C composed of a thermoplastic resin, or the like.
  • the intermediate layer contains a curable resin (for example, an ultraviolet curable resin, a thermosetting resin).
  • a curable resin for example, an ultraviolet curable resin, a thermosetting resin.
  • Such an intermediate layer may be a resin film containing a curable resin, a layer containing a curable pressure-sensitive adhesive D, or the like.
  • the thickness of the intermediate layer is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 40 ⁇ m, and further preferably 1.5 ⁇ m to 30 ⁇ m. Within such a range, an intermediate layer that functions well as a gas barrier layer can be formed.
  • the water vapor permeability of the intermediate layer is preferably 5000 g / (m 2 ⁇ day) or less, more preferably 4800 g / (m 2 ⁇ day) or less, and further preferably 4500 g / (m 2 ⁇ day) or less. It is more preferably 4200 g / (m 2 ⁇ day) or less. Within such a range, the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. While higher water vapor permeability of the intermediate layer is preferably small, its lower limit is, for example, 0.1g / (m 2 ⁇ day) .
  • the piercing strength of the intermediate layer is preferably 300 mN to 5000 mN, more preferably 500 mN to 4500 mN, and further preferably 1000 mN to 4000 mN.
  • the intermediate layer functions well as a gas barrier layer, and the shape change due to gas generation preferably occurs, and as a result, a deformed portion having an excellent shape is formed.
  • a small adherend for example, an electronic component
  • the ultraviolet transmittance of the intermediate layer at a wavelength of 360 nm is preferably 50% to 100%, more preferably 60% to 95%.
  • the intermediate layer as a resin layer is formed of, for example, a resin film.
  • the resin forming the resin film include polyethylene terephthalate resin, polyolefin resin, styrene elastomer resin (for example, SEBS), ultraviolet curable resin, thermosetting resin, urethane resin, epoxy resin and the like. Can be mentioned.
  • the resin film is made of a thermoplastic resin.
  • the thickness of the resin film is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.5 ⁇ m to 30 ⁇ m, and further preferably 1 ⁇ m to 20 ⁇ m.
  • Intermediate layer as a layer having adhesiveness
  • the intermediate layer as a layer having adhesiveness
  • an intermediate layer containing the curable pressure-sensitive adhesive D is arranged.
  • the pressure-sensitive adhesive layer containing the pressure-sensitive pressure-sensitive adhesive A and the intermediate layer containing the curable pressure-sensitive adhesive D are combined as the pressure-sensitive adhesive layer, a pressure-sensitive adhesive sheet capable of forming a better deformed portion by laser light irradiation. Can be obtained.
  • the curable pressure-sensitive adhesive D the pressure-sensitive adhesive described in Section C-2 can be used.
  • the thickness of the intermediate layer as the adhesive layer is preferably 5 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 30 ⁇ m.
  • the adhesive sheet of the present invention can be produced by any suitable method.
  • a composition for forming a gas generation layer containing a pressure-sensitive adhesive A and an ultraviolet absorber is directly applied onto a predetermined base material to form a gas generation layer, and the gas generation layer is formed.
  • a method of forming a pressure-sensitive adhesive layer by applying a composition for forming a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive B can be mentioned.
  • a composition for forming an intermediate layer is applied onto the gas generating layer to form the intermediate layer before forming the pressure-sensitive adhesive layer, and the intermediate layer is formed.
  • the pressure-sensitive adhesive layer forming composition is applied onto the pressure-sensitive adhesive layer to form the pressure-sensitive adhesive layer. Further, each layer may be formed separately and then bonded to form an adhesive sheet.
  • any appropriate coating method can be adopted. For example, after application, it can be dried to form each layer.
  • the coating method include a coating method using a multi-coater, a die coater, a gravure coater, an applicator, and the like.
  • the drying method include natural drying and heat drying. The heating temperature for heat-drying can be set to any suitable temperature depending on the characteristics of the substance to be dried. Further, depending on the morphology of each layer, activation energy ray irradiation (for example, ultraviolet irradiation) can be performed.
  • the method for processing electronic components of the present invention is to attach the electronic components to the adhesive sheet and to irradiate the adhesive sheet with laser light to peel off the electronic components from the adhesive sheet.
  • Examples of electronic components include semiconductor chips, LED chips, MLCCs, and the like.
  • the peeling of the electronic components can be performed regioselectively. Specifically, a plurality of electronic components may be attached and fixed to an adhesive sheet, a part of the electronic component may be peeled off, and the other electronic components may be peeled off so as to remain fixed. ..
  • the method for processing an electronic component of the present invention is to perform a predetermined process on the electronic component after the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet.
  • processing is not particularly limited, and for example, processing such as grinding processing, dicing processing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, arrangement, repair, and device surface protection. Can be mentioned.
  • the electronic component size (the area of the bonded surface) is, for example, 1 ⁇ m 2 ⁇ 250000 ⁇ m 2. In one embodiment, the size of the electronic component (the area of the bonded surface) the electronic component of 1 ⁇ m 2 ⁇ 6400 ⁇ m 2 may be subjected to treatment. In another embodiment, electronic components having an electronic component size (area of attachment surface) of 1 ⁇ m 2 to 2500 ⁇ m 2 may be subjected to processing.
  • a plurality of electronic components can be arranged on the adhesive sheet.
  • the spacing between electronic components is, for example, 1 ⁇ m to 500 ⁇ m.
  • it is advantageous in that the object to be processed can be temporarily fixed by narrowing the interval.
  • UV laser light for example, UV laser light can be used.
  • the irradiation output of the laser light is, for example, 1 ⁇ J to 1000 ⁇ J.
  • the wavelength of the UV laser light is, for example, 240 nm to 380 nm.
  • the method for processing an electronic component includes arranging the electronic component on another sheet (for example, an adhesive sheet, a substrate, etc.) after the electronic component is peeled off.
  • another sheet for example, an adhesive sheet, a substrate, etc.
  • the transmission spectrum of the layer alone was obtained.
  • the transmittance of the obtained transmission spectrum at wavelengths of 360 nm and 500 nm was extracted.
  • (2) Maximum gas generation peak temperature About 0.5 mg of the pressure-sensitive adhesive sheet sample was set in a heating furnace type pyrolyzer, and a mass chromatogram was obtained by EGA-MS analysis in which the components volatilized by heating were mass-analyzed.
  • a heating furnace type pyrolyzer (manufactured by Frontier Lab, trade name "PY2020iD”) raises the temperature from 40 ° C to 500 ° C at a heating rate of 10 ° C / min, and a GC / MS analyzer (manufactured by JEOL, trade name "JMS").
  • the generated gas species was identified.
  • Water vapor permeability A sample is prepared by pasting a sample so as to cover the opening of an Al jig having an opening of 10 mm ⁇ 10 mm, and a water vapor permeability measuring device (manufactured by MOCON, trade name “PERMATRAN-” A measurement sample was placed between the first chamber and the second chamber of W3 / 34G ”) and evaluated by the MOCON measurement method.
  • the temperature and humidity conditions were 30 ° C./90% RH, the gas (water vapor) flow rate was 10.0 ⁇ 0.5 cc / min, and the measurement time was 20 hours.
  • the water vapor transmittance was measured for each of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer, and the intermediate layer.
  • the surface of the pressure-sensitive adhesive layer (the surface of the gas-generating layer in Example 1 and Comparative Example 1) corresponding to any one spot that was pulse-scanned was observed with a confocal laser scanning microscope 24 hours after the laser beam irradiation, and was vertically displaced.
  • Y and horizontal displacement X (diameter; half-value full width) were measured.
  • the displacement Y is 8 ⁇ m or more, the peelability is remarkably excellent ( ⁇ in the table); when the displacement Y is 0.6 ⁇ m or more and less than 8 ⁇ m, the peelability is good ( ⁇ in the table); When is less than 0.6 ⁇ m, the peelability is insufficient (x in the table).
  • Adhesive strength (gas generation layer side) PET # 25 was attached to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet to obtain a measurement sample.
  • the adhesive force of the measurement sample to the SUS430 on the gas generation layer side was measured by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °).
  • Adhesive strength (adhesive layer) PET # 25 was attached to the gas generating layer side of the pressure-sensitive adhesive sheet to obtain a measurement sample.
  • the adhesive strength of the measurement sample to the SUS430 on the adhesive layer side was measured by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °). (12) In-plane uniformity of deformation The gas generating layer was irradiated with UV laser light as described in (8) above. Observe the deformed part in the 2 mm ⁇ 2 mm range randomly selected with a microscope, and if 90% or more of the convex parts are the same size, it is good ( ⁇ in the table), 80% or more and less than 90% of the convex parts.
  • Triboindenter TI-950 Triboindenter TI-950
  • a single indentation method at a predetermined temperature 25 ° C.
  • the elastic modulus was measured under the measurement conditions at a depth of about 1500 nm.
  • composition a for forming a gas generating layer In toluene, 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of ethyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, and 5 parts by weight of methyl methacrylate are contained. After adding 0.2 parts by weight of benzoyl peroxide as a polymerization initiator, the mixture was heated to 70 ° C. to obtain a toluene solution of an acrylic copolymer (polymer A).
  • a toluene solution of polymer A (polymer A: 100 parts by weight), an isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”) 1.5 parts by weight, and an ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477”).
  • Structure: [Chemical formula 1]) 20 parts by weight was mixed to prepare a composition a for forming a gas generating layer.
  • the composition of the composition a for forming a gas generating layer is shown in Table 1.
  • composition for forming a gas generating layer b A composition for forming a gas generating layer b was prepared in the same manner as in Production Example 1 except that the amount of the UV absorber was 10 parts by weight.
  • the composition of the gas generating layer forming composition b is shown in Table 1.
  • composition c for forming a gas generating layer As a UV absorber, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1, The composition c for forming a gas generation layer was prepared in the same manner as in Production Example 1 except that 10 parts by weight of 3,5-triazine (trade name "TINUVIN 460", manufactured by BASF, structure: [Chemical Formula 2]) was used. Prepared. The composition of the gas generating layer forming composition c is shown in Table 1.
  • composition d for forming a gas generating layer As a UV absorber, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl)- 20 parts by weight of the reaction product of 5-hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxylane (trade name "TINUVIN 400", manufactured by BASF, structure: [Chemical Formula 3]).
  • a composition d for forming a gas generating layer was prepared in the same manner as in Production Example 1 except that it was used.
  • the composition of the composition d for forming a gas generation layer is shown in Table 1.
  • composition e for forming a gas generating layer In ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of methyl acrylate, 10 parts by weight of acrylic acid, and benzoyl peroxide as a polymerization initiator After adding 0.2 parts by weight, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer B).
  • composition f for forming a gas generating layer In ethyl acetate, 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator are added. After the addition, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer C).
  • composition g for forming a gas generating layer In ethyl acetate, 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator are added. After the addition, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer C).
  • Ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 0.1 part by weight of epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C”), and ultraviolet absorber (manufactured by BASF, Inc., 20 parts by weight (trade name "Tinuvin 477”)) was mixed to prepare a composition g for forming a gas generating layer.
  • the composition of the composition g for forming the gas generation layer is shown in Table 3.
  • the composition of the composition h for forming the gas generation layer is shown in Table 3.
  • composition i for Forming Gas Generation Layer 100 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, and 0.2 parts by weight of benzoyl peroxide as a polymerization initiator were added to toluene. Then, it was heated to 70 ° C. to obtain a toluene solution of an acrylic copolymer (polymer D).
  • a toluene solution of polymer D (polymer D: 100 parts by weight), 0.1 part by weight of an epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C”), and an ultraviolet absorber (manufactured by BASF, product).
  • the composition i for forming a gas generating layer was prepared by mixing with 20 parts by weight of the name “Tinuvin 400”).
  • the composition of the composition i for forming a gas generation layer is shown in Table 3.
  • Ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 0.1 part by weight of epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C”), and ultraviolet absorber (manufactured by BASF, Inc., 20 parts by weight (trade name "Tinuvin 400”)) was mixed to prepare a composition i for forming a gas generating layer.
  • the composition of the composition j for forming a gas generation layer is shown in Table 3.
  • composition k for forming a gas generating layer In toluene, 50 parts by weight of butyl acrylate, 50 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, and 0. After adding 1 part by weight, 0.3 part by weight of trimethylolpropane triacrylate, and 0.1 part by weight of benzoyl peroxide as a polymerization initiator, the mixture is heated to 70 ° C. to obtain an acrylic copolymer (polymer E). A toluene solution was obtained.
  • a toluene solution of polymer E (polymer E: 100 parts by weight), 0.1 part by weight of an epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C”), and an ultraviolet absorber (manufactured by BASF, product).
  • the composition i for forming a gas generating layer was prepared by mixing with 20 parts by weight of the name “Tinuvin 400”).
  • the composition of the composition k for forming a gas generation layer is shown in Table 3.
  • Adhesive I was prepared in the same manner as in Production Example 10 except that the amount of the cross-linking agent blended was 1 part by weight and no surfactant was contained.
  • the composition of the pressure-sensitive adhesive I is shown in Table 2.
  • composition a for forming an intermediate layer An ethyl acetate solution of an acrylic copolymer (polymer B) was obtained in the same manner as in Production Example 5.
  • Ethyl acetate solution of polymer B (polymer B: 100 parts by weight), epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "Tetrad C"), 1 part by weight, UV oligomer (manufactured by Mitsubishi Chemicals, trade name "Shikou” UV-1700B ”) 50 parts by weight and 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name” Omnirad 127 ”) were mixed to prepare a composition a for forming an intermediate layer.
  • the composition of the intermediate layer forming composition a is shown in Table 3.
  • SEBS styrene moiety / ethylene /
  • Example 1 The composition a for forming a gas generating layer obtained in Production Example 1 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying).
  • the film was applied so as to have a thickness of 7 ⁇ m, and then dried to obtain an adhesive sheet consisting only of a gas generating layer on the polyethylene terephthalate film.
  • the obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 4.
  • Example 2 The pressure-sensitive adhesive a obtained in Production Example 10 is applied to a polyethylene terephthalate film (thickness: 75 ⁇ m) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) is 15 ⁇ m, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
  • the composition a for forming a gas generating layer obtained in Production Example 1 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying).
  • the pressure-sensitive adhesive layer precursor layer a and the gas generation layer precursor layer a are laminated and bonded between rolls, and a pressure-sensitive adhesive sheet (adhesive layer / gas generation layer) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. ) was obtained.
  • the obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 4.
  • Example 3 The pressure-sensitive adhesive a obtained in Production Example 10 is applied to a polyethylene terephthalate film (thickness: 75 ⁇ m) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) is 15 ⁇ m, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
  • the composition a for forming an intermediate layer obtained in Production Example 12 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying) is increased.
  • the film was applied to a thickness of 15 ⁇ m and then dried to form an intermediate layer precursor layer a on the polyethylene terephthalate film.
  • the pressure-sensitive adhesive layer precursor layer a and the intermediate layer precursor layer a are laminated and bonded between rolls , and UV-irradiated from the intermediate layer precursor layer side under the condition of 500 mJ / cm 2 , and treated with a silicone release agent.
  • a laminate precursor layer a sandwiched between surfaced polyethylene terephthalate films was obtained.
  • composition a for forming a gas generating layer obtained in Production Example 1 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying).
  • a silicone release agent-treated surface manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m
  • the thickness after solvent volatilization (drying) was applied so as to have a thickness of 7 ⁇ m, and then dried to form a gas generation layer precursor layer a on the polyethylene terephthalate film.
  • the intermediate layer precursor layer a of the laminate precursor layer a and the gas generation layer precursor layer a are separated.
  • Example 4 The pressure-sensitive adhesive a obtained in Production Example 10 is applied to a polyethylene terephthalate film (thickness: 75 ⁇ m) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) is 15 ⁇ m, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
  • the composition b for forming an intermediate layer obtained in Production Example 13 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying) is increased.
  • the film was applied to a thickness of 15 ⁇ m and then dried to form an intermediate layer precursor layer a on the polyethylene terephthalate film.
  • the pressure-sensitive adhesive layer precursor layer a and the intermediate layer precursor layer b were laminated and bonded between rolls to obtain a laminate precursor layer b sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. ..
  • the composition a for forming a gas generating layer obtained in Production Example 1 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying).
  • Example 5 The pressure-sensitive adhesive a obtained in Production Example 10 is applied to a polyethylene terephthalate film (thickness: 75 ⁇ m) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) is 15 ⁇ m, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
  • the composition a for forming a gas generating layer obtained in Production Example 1 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 ⁇ m), and the thickness after solvent volatilization (drying).
  • the adhesive layer precursor layer a was laminated between rolls on one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror # 2F51N", thickness: 2 ⁇ m). Next, the gas generating layer precursor layer a was laminated and bonded between the rolls on the side opposite to the pressure-sensitive adhesive layer precursor layer a of the polyethylene terephthalate film.
  • Example 6 An adhesive sheet was obtained in the same manner as in Example 5 except that the gas generating layer forming composition b was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 5.
  • Example 7 An adhesive sheet was obtained in the same manner as in Example 5 except that the gas generating layer forming composition c was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 5.
  • Example 8 An adhesive sheet was obtained in the same manner as in Example 5 except that the gas generating layer forming composition d was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 5.
  • Example 9 An adhesive sheet was obtained in the same manner as in Example 5 except that the gas generating layer forming composition e was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 5.
  • Example 10 An adhesive sheet was obtained in the same manner as in Example 5 except that the gas generating layer forming composition f was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 5.
  • Example 11 An adhesive sheet was obtained in the same manner as in Example 1 except that the gas generating layer forming composition g was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.
  • Example 12 An adhesive sheet was obtained in the same manner as in Example 1 except that the gas generating layer forming composition h was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.
  • the pressure-sensitive adhesive I is used instead of the pressure-sensitive adhesive a, the thickness of the pressure-sensitive adhesive layer is 10 ⁇ m, a PET film having a thickness of 188 ⁇ m is used as an intermediate layer, and a heat-expandable microsphere is contained instead of the composition a for forming a gas generating layer.
  • a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5 except that a 48 ⁇ m gas generating layer was formed using Composition II. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 7.
  • the pressure-sensitive adhesive I is used instead of the pressure-sensitive adhesive a, the thickness of the pressure-sensitive adhesive layer is 10 ⁇ m, a PET film having a thickness of 100 ⁇ m is used as an intermediate layer, and a heat-expandable microsphere is contained instead of the composition a for forming a gas generating layer.
  • a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5 except that a 48 ⁇ m gas generating layer was formed using Composition III. The obtained adhesive sheet was subjected to the above evaluations (1) to (13). The results are shown in Table 7.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
PCT/JP2020/044512 2019-12-20 2020-11-30 粘着シート WO2021124855A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020227020301A KR20220117232A (ko) 2019-12-20 2020-11-30 점착 시트
CN202080088628.5A CN114846098A (zh) 2019-12-20 2020-11-30 粘合片
JP2021565431A JPWO2021124855A1 (zh) 2019-12-20 2020-11-30

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-230601 2019-12-20
JP2019230601 2019-12-20
JP2020-114046 2020-07-01
JP2020114046 2020-07-01

Publications (1)

Publication Number Publication Date
WO2021124855A1 true WO2021124855A1 (ja) 2021-06-24

Family

ID=76478669

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/044512 WO2021124855A1 (ja) 2019-12-20 2020-11-30 粘着シート

Country Status (5)

Country Link
JP (1) JPWO2021124855A1 (zh)
KR (1) KR20220117232A (zh)
CN (1) CN114846098A (zh)
TW (2) TWI767453B (zh)
WO (1) WO2021124855A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024566A1 (ja) * 2022-07-25 2024-02-01 株式会社レゾナック 仮固定用フィルム、仮固定用積層体、半導体装置の製造方法、及び仮固定用組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6151140A (ja) * 1984-08-21 1986-03-13 Fuji Photo Film Co Ltd 熱現像感光材料
JP2004186200A (ja) * 2002-11-29 2004-07-02 Sekisui Chem Co Ltd 半導体チップの製造方法
JP2010202833A (ja) * 2009-03-05 2010-09-16 Sekisui Chem Co Ltd 電子部品加工用粘着テープ
WO2011118488A1 (ja) * 2010-03-24 2011-09-29 積水化学工業株式会社 接着剤組成物及び接着テープ
JP2019070104A (ja) * 2017-10-06 2019-05-09 積水化学工業株式会社 表面保護フィルム
WO2020054146A1 (ja) * 2018-09-10 2020-03-19 昭和電工株式会社 粘着シート

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3594853B2 (ja) 1999-11-08 2004-12-02 日東電工株式会社 加熱剥離型粘着シート
JP2013159743A (ja) * 2012-02-07 2013-08-19 Nitto Denko Corp 粘着剤積層物の剥離方法およびそれに用いる粘着剤層
JP6054208B2 (ja) * 2013-03-04 2016-12-27 日東電工株式会社 熱剥離型粘着シート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6151140A (ja) * 1984-08-21 1986-03-13 Fuji Photo Film Co Ltd 熱現像感光材料
JP2004186200A (ja) * 2002-11-29 2004-07-02 Sekisui Chem Co Ltd 半導体チップの製造方法
JP2010202833A (ja) * 2009-03-05 2010-09-16 Sekisui Chem Co Ltd 電子部品加工用粘着テープ
WO2011118488A1 (ja) * 2010-03-24 2011-09-29 積水化学工業株式会社 接着剤組成物及び接着テープ
JP2019070104A (ja) * 2017-10-06 2019-05-09 積水化学工業株式会社 表面保護フィルム
WO2020054146A1 (ja) * 2018-09-10 2020-03-19 昭和電工株式会社 粘着シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024566A1 (ja) * 2022-07-25 2024-02-01 株式会社レゾナック 仮固定用フィルム、仮固定用積層体、半導体装置の製造方法、及び仮固定用組成物

Also Published As

Publication number Publication date
TW202126767A (zh) 2021-07-16
JPWO2021124855A1 (zh) 2021-06-24
TWI824509B (zh) 2023-12-01
TWI767453B (zh) 2022-06-11
CN114846098A (zh) 2022-08-02
TW202233780A (zh) 2022-09-01
KR20220117232A (ko) 2022-08-23

Similar Documents

Publication Publication Date Title
CN113652174A (zh) 粘合片
JP6873354B1 (ja) 粘着シート
WO2021131518A1 (ja) 粘着シート
WO2021124855A1 (ja) 粘着シート
WO2021220662A1 (ja) 粘着シート
WO2021131735A1 (ja) 粘着シート
WO2021124854A1 (ja) 粘着シート
WO2021220663A1 (ja) 粘着シート
WO2022044441A1 (ja) 部材加工方法
JP6890216B1 (ja) 粘着シート
WO2021124856A1 (ja) 粘着シート
WO2022118499A1 (ja) 粘着シート
JP2021155690A (ja) 粘着シート
TW202313335A (zh) 電子零件暫時固定用黏著片材及電子零件之處理方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20901323

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021565431

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20901323

Country of ref document: EP

Kind code of ref document: A1